Description du sujet de thèse

Phosphonium ylides, also known as Wittig reagents, are important synthetic tools. In the 60s, Ramirez et al. prepared the first carbodiphosphoranes, which are actually phosphonium bis-ylides.[1] Recent studies have shown that these bis-ylides can be considered as sources of atomic carbon (an elementary carbon atom complexed by 2 phosphine ligands).
Depending on the nature of ligands used, the chemical nature of central carbon of bis-ylides can be modified and introduced as “atomic carbon” into various organic molecules.. Our research team has contributed to the development of this chemistry with the preparation of dissymmetric (phosphine/sulfide) or symmetric (bis sulfides) bis-ylides.[2,3]. For the latter model, since sulfide ligands are very labile, atomic carbon can be spontaneously released depending on the operating conditions.
We wish, in the course of this thesis, to take advantage of our experience in ylide-chemistry to develop further the bis-ylide chemistry and to exploit these atomic sources in organic chemistry or for materials.
This PhD will be supported by an ANR fellowship and developed in collaboration with experts of theoretical investigation (V. Branchadell, UAB, Barcelona) and materials (E. Flahaut, CIRIMAT, University of Toulouse) in order to tackle this challenging project.

The candidate must have a solid background in molecular chemistry. Some experience in manipulation of highly sensitive species would be appreciated. This subject will lead the PhD student to achieve a wide formation in organic-, theoretical- and material-chemistry and ability to use a large variety of techniques (NMR, IR, MS, GC…) for the characterization of new compounds.

We are looking for a motivated candidate able to work as part of a team. To apply, please send us a CV, a motivation letter and the name of at least 2 reference persons.

Fellowship available (gross salary 2200 € per month). PhD starting 2025 October 1st.

[1] F. Ramirez, N. B. Desai, B. Hansen, N. McKelvie, J. Am. Chem. Soc., 1961, 83, 3539.
[2] a) N. Dellus, T. Kato, X. Bagan, N. Saffon-Merceron, V. Branchadell, A. Baceiredo, Angew. Chem., Int. Ed., 2010, 49(38), 6798; b) N. Dellus, T. Kato, N. Saffon-Merceron, V. Branchadell, A. Baceiredo, Inorg. Chem. 2011, 50, 7949
[3] a) U. Authesserre, V. S. Swamy, N. Saffon-Merceron, A. Baceiredo, T. Kato, E. Maerten, Molecules 2023, 28, 3295; b) S. Hameury, L. Bousquet, N. Saffon-Merceron, A. Baceiredo, D. Madec, E. Maerten, Dalton Trans., 2025, 54, 4142.

Contexte de travail

LHFA, mixed unit CNRS-UPS located within the chemistry building of the Université Paul Sabatier, 118 route de Narbonne, Toulouse.
The LHFA is constituted of 6 research teams , with roughly 60 persons. The main theme is directed toward the study of original molecules and complexes, highly reactive. It is a member of the "Institut de Chimie de Toulouse" (Toulouse Institute of Chemistry). The research project is founded by ANR. The PhD will join ECOIH's TEAM, constituted by 4 permenent researchers. the PhD candidate will actively contribute to the development of the research and be included in a scientifically rich and dynamic environment.